DE1260684B - Process for the production of threads and fibers from polyamides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
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DOIf

German class: 29 b -3/60

1 260 684
F41969IVc / 29b
February 8, 1964
February 8, 1968

In the polycondensation of ammonium salts of diamines with dicarboxylic acids or in the Polymerization of lactams results in more or less high molecular weight polyamides, their water absorption at room or elevated temperature on the number of carbon atoms or heteroatoms in the Monomer unit depends. So has z. B. the polyamide from hexamethylenediamine and sebacic acid a lower water absorption capacity than the polyamide made from hexamethylenediamine and adipic acid or caprolactam. The hydrophilicity can also be increased by incorporating them Ammonium salts containing heteroatoms such as oxygen. The starting components are used here z. B. the ammonium salts from ether dicarboxylic acid or ether diamines, z. B. y, / - di- (amino-propoxy) -butane - (- ethane, -hexane) or the corresponding y, / - di- (carboxy-propoxy) -alkylenes.

For the dyeability with basic dyes and to increase the hydrophilicity were also already proposed diamines which sit on an aromatic nucleus via alkylene groups and additionally contain a sulfonic acid group (Belgian patent 596 144).

This includes B. the di- (aminomethyl) -benzenesulfonic acid sodium. Located at the one here The above-mentioned class of compounds, the amino group directly on the benzene nucleus, is obtained in the condensation with dicarboxylic acids in the presence of the usual starting materials leading to polyamides Polyamides that are discolored dark brown.

It has now been observed that when using certain diaminodiarylsulfonic acids, in which the amino group is bonded directly to the aromatic nucleus, such problems do not occur. The invention therefore relates to a process for the production of threads and fibers from polyamides after 'the melt spinning process, which is characterized in that sulfonic acid group-containing Polyamides used by polycondensation of 4,4'-diamino-2,2'-diphenyldisulfonic acids or 4,4'-diamino-2,2'-diphenylalkanedisulfonic acids of the formula

H, N

(CH ₂ ),

NH,

SOoMe

SO, Me

wherein χ denotes the numbers from 0 to 3 and Me denotes hydrogen or an alkali metal, and alkylenedicarboxylic acids or their alkali salts in amounts up to processes for the production of threads and fibers from polyamides

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

Named as inventor:

Dr. Otto Unger, 6086 Goddelau;

Dr. Günter Nawrath,

Dr. Günther Nischk, 4047 Dormagen

20 percent by weight with polyamide-forming starting materials have been produced.

As diaminosulfonic acids which are suitable for the process according to the invention are, for. B. 4,4'-diamino - 2,2'-diphenyldisulfonic acid, 4,4'-diamino-2,2'-dibenzyldisulfonic acid, 4,4'-diamino-2,2'-diphenylpropanedisulfonic acid and 4,4'-diamino-2-diphenylsulfonic acid called. These compounds exist as internal ammonium salts. In the case of polycondensation of the polyamide-forming starting materials are now either these inner ammonium salts in combination used with dialkali salts of dicarboxylic acid, or the internal ammonium salts are carried out of the sulfonic acids into the corresponding alkali salts and condenses in the presence of the free dicarboxylic acid. Succinic acid, adipic acid, Called suberic acid and sebacic acid. To high polymer, well spinnable polyamides too obtained, it is advantageous to mix the sulfo-containing diamines with the equivalent amount of dicarboxylic acid or to use their alkali salts.

For the polycondensation, the internal ammonium salts mentioned or their alkali salts are used in Combination with the appropriate amount of dicarboxylic acid or its alkali metal salts are known Starting materials for polyamide production added in amounts of 0.1 to 20%. The addition itself can be done so that the sulfonic acid group-containing diamines with the dicarboxylic acids in solid form or - which is particularly favorable - that one adds the equivalent amount of the internal Adds ammonium salts or alkali salts and the dicarboxylic acids or their salts in aqueous solution. This ensures that the monomers are finely distributed in the polyamide melt. When heating up

809 507/613

these mixtures soon go into the clear state, with the condensation in parallel with it the polyamide runs.

Lactams, such as caprolactam, and also ω-aminocarboxylic acids, such as ε- aminocaproic acid, 11-aminoundecanoic acid and the diammonium salts of alkylenediamine with aliphatic dicarboxylic acids, such as tetra- , Octamethylenediamine and glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

The condensation itself is carried out at temperatures above the melting points of the polyamides, preferably between 250 and 300 ^° C. If the condensation is not carried out under pressure, it is advisable to pass inert gases, such as carbonic acid or nitrogen, over the melt. When using caprolactam as the starting material, it is also advantageous to carry out an extraction with water before melt spinning in order to remove monomeric lactam. The polyamides containing sulfonic acid groups obtained in this way are obtained in colorless form and can be converted into threads and fibers by the known methods of melt spinning. As a result of their greater hydrophilicity, they have the ability to bind more water than the unmodified starting polyamides. In addition, when the abovementioned diamines containing sulfonic acid groups are used, they are stable to light.

It is surprising that the diamines containing sulfonic acid groups used according to the invention Condense easily and without discoloration into the polyamides, even though they are aromatically bound Contain amino groups. If, on the other hand, is z. B. an alkyl or alkoxy group in the aromatic Phenyl nucleus, a stronger discoloration already occurs during condensation. The same applies those diaminodiarylsulfonic acids of the above constitution in which the sulfonic acid groups are in the 3 position.

example 1

3.04 parts of 4,4'-diaminodibenzyldisulfonsaures-2,2 'potassium are 0.96 parts of adipic acid, 10 parts of ε-aminocaproic acid and 186 parts of caprolactam under a stream of pure nitrogen and stirring for 30 minutes 25O ⁰ C and then 5 hours heated to 300 ^{0 C.} A highly viscous, colorless melt is created. After the melt has been crushed, the chips are extracted with water. After drying at a moisture content of 0.061%, the chips have a relative viscosity of 3.20 and a pour point of 220 to 221 ° C.

The threads obtained from the above chips have a good hydrophilicity and affinity for basic ones Dyes; the ■ spinning temperature is 270 ° C; Take-off: 600 m / min.

The approaches described in Table 1 are carried out analogously.

Tabel

Melt viscosity in poise ReI.
in "/ ο

HäO content of
Schnitzel in%

Fp.

7.60 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 '

potassium

2.40 parts of adipic acid
10.00 parts of ε-aminocaproic acid, 180.00 parts of caprolactam

15.20 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 '

potassium

4.80 parts of adipic acid
10.00 parts of ε-aminocaproic acid 170.00 parts of caprolactam

7.40 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 '

sodium

2.60 parts of adipic acid
20.00 parts of ε-aminocaproic acid 170.00 parts of caprolactam

3.04 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 '

potassium

0.96 parts of adipic acid
10.00 parts of ε-aminocaproic acid 186.00 parts of caprolactam

Example 2

To a mixture consisting of 2.5 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 ', 10 parts ε-aminocaproic acid and 186 parts of caprolactam are 1.5 parts of potassium dipate in a little water solved added. This mixture is under 3 330

3 030

2,860

10 300

2.69

2.58

2.68

3.20

0.069

0.081

0.081

0.061

218 to 219

212 to 213

214 to 217

220 to 221

passing over pure nitrogen with stirring for minutes at 250 ^° C. and then heated for 5 hours to 300 ^° C., a highly viscous, colorless melt being formed. The melt is crushed and water is used to remove the monomer from the chips. After drying, the chips have a moisture content of 0.016%

Viscosity of 3.26 and the pour point of 222 to 225 ^: C.

The threads obtained from these chips by melt spinning have a good affinity for basic dyes and hydrophilicity; the spinning temperature is 270 ° C; Take-off: 600 m / min. The tests listed in Table 2 are carried out according to this rule.

Tabel

2.50 parts of 4,4'-diaminodibenzyldisulfonic acid-2.2 '1.50 parts of potassium adipate
10.00 parts of .'-aminocaproic acid
186.00 parts of caprolactam

6.25 parts 4,4'-diaminodibenzyldisulfonic acid-2.2 '3.75 parts potassium adipate
10.00 parts of f-aminocaproic acid
180.00 parts of caprolactam

12.50 parts of 4,4'-diaminodibenzyldisulfonic acid-2,2 '7.50 parts of potassium adipate
10.00 parts aminocaproic acid
170.00 parts of caprolactam

Melt viscosity in poise

20 200

1860

837

3.26

2.54

2.19

HaO content of
Schnitzel in%

Fp.

0.016

0.074

0.073

222 to 225

216 to 218

206 to 209

Example 3

The mixture, consisting of 3.53 parts of 4,4'-diaminodiphenyldisulfonic acid-2,2'Lithium, 1.47 parts of adipic acid, 10 parts; -aminocaproic acid and 185 parts of caprolactam, is passed over with pure nitrogen and stirring for 30 minutes 250C and then heated to 300C for 5 hours, resulting in a highly viscous, colorless melt arises. After the melt has been comminuted, water is used to remove the monomer from the chips; the schnitzels are then dried. With a moisture content of 0.01 "/ 0, these schnitzel have the viscosity of 2.91 and the pour point of 219 to 220 ° C.

The threads obtained from these chips by melt spinning have a good affinity for basic dyes and good hydrophilicity; the spinning temperature is 270 "C: Discharge: 600 m / min.

Correspondingly carried out polycondensations lead to polyamides with those listed in Table 3 Data.

Tabel

Enamel
viscosity
in poise ReI.
in % H ₂ O content of
Schnitzel in% Fp. 3.53 parts of 4,4'-diaminodiphenyldisulfonic acid-2,2 '
lithium
1.47 parts of adipic acid
10.00 parts aminocaproic acid
185.00 parts of caprolactam 4140 C 2.91 0.010 219 to 220 7.04 parts of 4,4'-diaminodiphenyldisulfonic acid-2,2 '
lithium
2.96 parts of adipic acid
10.00 parts (-aminocaproic acid
180.00 parts of caprolactam 2160 2.41 0.0i8 215 to 218 13.67 parts of 4,4'-diaminodiphenyldisulfonic acid-2,2 '
lithium
6.33 parts of adipic acid
10.00 parts (-aminocaproic acid
170.00 parts of caprolactam 785 2.02 0.070 208 to 210

Example 4 pure nitrogen and stirring for 30 minutes

A mixture consisting of 2.75 parts 4,4'-di-250 ^° C. and then 5 hours at 300 ° C.

aminodiphenyldisulfonic acid-2,2 ', 1.25 parts Li heated. The melt is viscous and colorless. the

thium adipate, 10 parts / -aminocaproic acid and 65 melt is converted into schnitzel, and these

186 parts of caprolactam, the monomer is removed with water while passing over. To

drying the shreds to a moisture content of 0.01%, they have the viscosity of 2.91 and the yield point of 219-220 ⁰ C.

The threads spun from these chips by melt spinning show a good affinity for alkaline substances

Dyes and hydrophilicity; the spinning temperature is 280 ⁰ C; Take-off: 600 m / min.

Polycondensations carried out accordingly lead to polyamides with those listed in Table 4 Data.

Table 4

Melt viscosity
in poise

ReI.
in %

H »O content of the schnitzel in ° / o

Fp.

2.75 parts 4,4'-diaminodiphenyldisulfonic acid-2,2 '1.25 parts lithium adipate
10.00 parts of ε-aminocaproic acid 186.00 parts of caprolactam

6.87 parts of 4,4 ^/ -diaminodiphenyldisulfonic acid-2.2 '3.13 parts of lithium adipate
10.00 parts of ε-aminocaproic acid, 180.00 parts of caprolactam

13.75 parts of 4,4'-diaminodiphenyldisulfonic acid-2.2 '6.25 parts of lithium adipate
10.00 parts of ε-aminocaproic acid 170.00 parts of caprolactam

5950

1820

1120

3.19

2.59

2.06

0.086

0.093

0.103

219 to 222

216 to 218

210

Claims (1)

Claim: Process for the production of threads and fibers from polyamides by the melt spinning process, characterized in that sulfonic acid group-containing polyamides are used, which by polycondensation of 4,4'-diamino-2,2'-diphenyldisulfonic acids or 4,4'-diamino-2,2'-diphenylalkanedisulfonic acids the formula H, N (CH ₂ ) _X SO ₁ Me SO ₃ Me NH ₂ wherein χ denotes the numbers from 0 to 3 and Me denotes hydrogen or an alkali metal, and alkylenedicarboxylic acids or their alkali salts in amounts up to 20 percent by weight with polyamide-forming Starting materials have been produced. 809 507/613 1.68 © Bundesdruckerei Berlin